JP4407798B2 - Ruthenium complex compound, production method thereof, catalyst for metathesis reaction and catalyst for hydrogenation reaction - Google Patents

Description

  The present invention relates to a novel ruthenium complex compound and a method for producing the same. The present invention also relates to a metathesis reaction catalyst and hydrogenation reaction catalyst for an olefin compound containing a specific ruthenium complex compound, and a method for producing a norbornene-based ring-opening polymer using the metathesis reaction catalyst.

  Metathesis reactions such as ring-opening metathesis polymerization, ring-closing metathesis reaction of olefin compounds, cross-metathesis reaction of acyclic olefins, and metathesis polymerization of acyclic dienes are industrially useful reactions. In recent years, a ruthenium complex compound in which a carbene compound is coordinated to ruthenium (hereinafter sometimes referred to as “ruthenium-carbene complex”) has attracted attention as a catalyst used in the metathesis reaction.

  In particular, ruthenium-carbene complex (complex I) having 1,3-dimesitylimidazolidin-2-ylidene as a ligand or ruthenium- having 1,3-dimesitylimidazoline-2-ylidene as a ligand It is known that a carbene complex (complex II) becomes a highly active catalyst for metathesis reactions (see, for example, Patent Documents 1 and 2). However, Complex I has a long process for synthesizing 1,3-disubstituted imidazolinium salts, which are raw materials for ligands, and has low production efficiency. On the other hand, the complex II is relatively easy to synthesize, but is easily soluble in a general organic solvent, so that isolation and purification by crystallization must be performed at a low temperature.

  In addition, a method for producing a ruthenium-carbene complex (complex III) having 1,3-dimesitylimidolin-2-ylidene substituted at the 4-position and 5-position with a chlorine atom as a ligand, and using the complex A ring-opening metathesis polymerization of 1,5-cyclooctadiene has also been reported (see Non-Patent Documents 1 and 2). However, the synthesis of Complex III requires the isolation and purification of the products in each reaction consisting of three steps, and the number of steps is extremely large.

Japanese translation of PCT publication No. 2003-500412 Special table 2002-524250 gazette Chemistry-A European Journal, 2001, Vol. 7, p. 3236-3253 Journal of American Chemical Society, 2003, vol. 125, p. 2546-2558

  An object of the present invention is to provide a ruthenium complex compound useful as a catalyst for metathesis reactions and hydrogenation reactions, and a simple and industrially advantageous production method for obtaining the same. Another object of the present invention is to provide a highly active metathesis reaction catalyst and hydrogenation reaction catalyst, and a process for producing a norbornene-based ring-opening polymer using the metathesis reaction catalyst.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have carried out the deprotonation step, the halogenation step, and the ligand exchange step with a ruthenium compound in a one-pot in a 1,3-disubstituted imidazolium salt. Can easily produce a ruthenium complex compound (A) having a substituted imidazoline-2-ylidene substituted with a halogen atom at positions 4 and 5 as a ligand, and a ruthenium complex obtained by using a specific organic solvent It was found that the compound can be easily isolated and purified. Further, the present inventors have found that the ruthenium complex compound (A) is useful as a catalyst for the metathesis reaction and hydrogenation reaction, and particularly shows high activity in the ring-opening metathesis polymerization reaction of norbornene monomers. Further, a ruthenium complex compound (A1) having a substituted imidazoline-2-ylidene substituted with a bromine atom at the 4-position and 5-position as a ligand is a novel compound, and the ruthenium complex compound (A1) has a polar group. It has been found that the present invention shows high activity in the ring-opening metathesis polymerization reaction of norbornene-based monomers, and the present invention has been completed based on these findings.

Thus, according to the present invention, there is provided a process for producing a ruthenium complex compound (A) having a substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with a halogen atom as a ligand, wherein the imidazolium salt is deprotonated. Deprotonation step for reacting with an agent, then halogen substitution step for adding a halogenating agent for reaction, and ligand exchange for adding a ruthenium compound having a neutral ligand to the resulting reaction product There is provided a method for producing a ruthenium complex compound, characterized in that the step is carried out in one pot.
Each of the above steps is preferably performed in the presence of an organic solvent in which the ruthenium complex compound (A) is soluble. Subsequent to the ligand exchange step, an organic solvent insoluble in the ruthenium complex compound (A) is added and the step is performed. It is more preferable to have a step of precipitating the ruthenium complex compound.

  According to the second aspect of the present invention, there is provided a ruthenium complex compound (A1) having, as a ligand, substituted imidazoline-2-ylidene substituted at the 4th and 5th positions with a bromine atom.

  According to 3rd this invention, the catalyst for metathesis reaction of the olefin compound formed by containing a ruthenium complex compound (A1) is provided. The metathesis reaction catalyst is preferably used for ring-opening metathesis polymerization of norbornene monomers.

  According to the fourth aspect of the present invention, there is provided a catalyst for ring-opening metathesis polymerization of a norbornene monomer containing the ruthenium complex compound (A).

  According to the fifth aspect of the present invention, there is provided a process for producing a norbornene-based ring-opening polymer, wherein the norbornene-based monomer is polymerized in the presence of the catalyst for ring-opening metathesis polymerization of the present invention. . The norbornene monomer is preferably one having a polar group.

  According to the sixth aspect of the present invention, there is provided a catalyst for hydrogenation reaction of an olefin compound comprising the ruthenium complex compound (A).

  According to the present invention, it is possible to easily and efficiently produce a ruthenium complex compound (A) having a substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with a halogen atom as a ligand. Among the ruthenium complex compounds (A), the ruthenium complex compound (A1) having a substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with a bromine atom as a ligand is a novel compound, particularly a polar group. It exhibits high activity as a catalyst for ring-opening metathesis polymerization of norbornene-based monomers having the above.

  The method for producing a ruthenium complex compound of the present invention is a method for producing a ruthenium complex compound (A) having a substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with a halogen atom as a ligand. A deprotonation step of reacting a salt with a deprotonating agent, a halogen substitution step of adding a halogenating agent to cause the reaction, and further adding a ruthenium compound having a neutral ligand to the obtained reaction product. A method for producing a ruthenium complex compound, wherein the ligand exchange step is performed in one pot. In the present invention, performing in one pot means performing the reaction continuously without isolating and purifying the reaction product of each step.

  Substituted imidazoline-2-ylidene in which the 4-position and the 5-position are substituted with a halogen atom is a compound represented by the general formula (1).

In formula (1), Y ¹ and Y ² represent a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Of these, chlorine and bromine are preferred because of their ease of synthesis, and bromine is most preferred because of its high catalytic activity in the polymerization reaction of monomers having polar groups.

R ¹ and R ² may each independently have a substituent containing at least one selected from a hydrogen or halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. A hydrocarbon group having 1 to 20 carbon atoms is represented. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The alkyl group, alkenyl group and alkynyl group may be linear, branched or cyclic. Examples of the substituent that the hydrocarbon group may have include a nitro group, a nitroso group, an alkoxyl group, an aryloxy group, an amide group, a carboxyl group, a carbonyl group, a silyl group, and a sulfonyl group.

As a hydrocarbon group, a C1-C20 alkyl group or a C6-C20 aryl group is preferable. Specifically, methyl group, ethyl group, isopropyl group, sec-butyl group, tert-butyl group, n-butyl group, n-pentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, etc. An alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a benzyl group, a 1-phenylethyl group, a 1-phenylpropyl group, a diphenylmethyl group, 1- Aralkyl groups having 7 to 20 carbon atoms such as (α-naphthyl) ethyl group and 1- (β-naphthyl) ethyl group; 1- (1,2,2-trimethylpropoxycarbonyl) ethyl group, 2- (1,2 , 2-trimethylpropoxycarbonyl) ethyl group, 1- (ethoxycarbonyl) ethyl group, 2- (ethoxycarbonyl) ethyl group and other functional groups such as 1 to 1 carbon atoms. 20 alkyl groups;
Phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-diisopropylphenyl group, mesityl group, 3, 5-dimethoxyphenyl group, 2-aminophenyl group, 4-aminophenyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 2-chlorophenyl group, 4-chlorophenyl group, 2-nitrophenyl group, 4-nitrophenyl And an aryl group having 6 to 20 carbon atoms which may have a substituent such as a group, 2-acetoxyphenyl group, 4-acetoxyphenyl group, α-naphthyl group and β-naphthyl group.
Among them, isopropyl group, cyclohexyl group, 1-phenylpropyl group, diphenylmethyl group, mesityl group, and 2,6-diisopropylphenyl group are particularly preferable.

  The ruthenium complex compound (A) according to the present invention is not particularly limited as long as it has a substituted imidazoline-2-ylidene substituted at the 4th and 5th positions with a halogen atom as a ligand. The ruthenium complex compound (A1) having a substituted imidazoline-2-ylidene substituted with a bromine atom as a ligand is preferable because it is highly active as a catalyst for the ring-opening metathesis reaction of a norbornene monomer having a polar group. As a specific structure thereof, a ruthenium-carbene complex compound represented by the general formula (2) is preferable because of its high activity.

In formula (2), R ¹ , R ² , Y ¹ and Y ² represent the same meaning as in general formula (1). X ¹ and X ² each independently represent any anionic ligand, and L represents any neutral ligand. m is 1 or 2, and n is 0 or 1.

R ³ and R ⁴ each independently represent a hydrogen atom or an organic group. R ³ or R ⁴ may be bonded to L to form a ring. Examples of the organic group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carboxy having 1 to 20 carbon atoms. Rate group, C1-C20 alkoxyl group, C2-C20 alkenyloxy group, C2-C20 alkynyloxy group, C6-C20 aryloxy group, C2-C20 alkoxycarbonyl Group, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, and an alkynylsulfinyl group having 1 to 20 carbon atoms. Further, these organic groups may be substituted with a group containing any atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom, or a halogen atom. Among these, it is preferable that one of R ³ and R ⁴ is a hydrogen atom and the other is the above organic group, one is a hydrogen atom and the other is an alkyl group having 1 to 20 carbon atoms, It is more preferable that they are a 2-20 alkenyl group, a C6-C20 aryl group, or a C1-C20 alkoxyl group.

The anionic ligands (X ¹ and X ² ) may be any ligands that have a negative charge when pulled away from the central metal (Ru). Further, the neutral ligand (L) may be any ligand as long as it has a neutral charge when it is separated from the central metal, and the 4-position and 5-position represented by the formula (1). May be substituted imidazoline-2-ylidene substituted with a halogen atom.

Specific examples of the anionic ligands (X ¹ and X ² ) include halogen atoms such as fluorine, chlorine, bromine and iodine; hydrogen atoms; diketonate groups such as acetylacetonate; Cyclopentadienyl group, allyl group, alkenyl group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, carboxyl group, alkyl sulfonate group, aryl sulfonate group which may have a substituent Examples include nate group, alkylthio group, alkenylthio group, arylthio group, alkylsulfonyl group, and alkylsulfinyl group. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

  Specific examples of the neutral ligand (L) include oxygen atom, water, carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, Examples include thioethers, amides, aromatic compounds, cyclic diolefins, olefins, isocyanides, thiocyanates, and heterocyclic carbene compounds. Among these, pyridines, phosphines, ethers, and heterocyclic carbene compounds are preferable, phosphines are more preferable, and tricyclohexylphosphine is particularly preferable.

  Preferred examples of the ruthenium complex compound (A) represented by the general formula (2) include compounds represented by the following general formulas (3) to (7) as m = 1 and n = 0. Can be mentioned.

  As what is m = 2 and n = 0, the compound represented by following General formula (8) is mentioned.

  As what is m = 1 and n = 1, the compound represented by following General formula (9) is mentioned.

In general formulas (3) to (9), R ¹ , R ² , Y ¹ and Y ² represent the same meaning as in general formula (1). Further, Ph a phenyl, PCy ₃ is tricyclohexylphosphine, Et is ethyl, i-Pr is isopropyl, Py is pyridine, t-Bu is a tert- butyl, respectively.

  Among the compounds represented by the above general formula, benzylidene (1,3-dimesityl-4,5-dibromoimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-diphenylmethyl-4,5 -Dibromoimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, ethoxymethylene (1,3-dimesityl-4,5-dibromoimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, ethoxymethylene (1,3 -Diphenylmethyl-4,5-dibromoimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, 2-phenylethylidene (1,3-dimesityl-4,5-dibromoimidazolin-2-ylidene) Down) (tricyclohexylphosphine) ruthenium dichloride, 2-phenyl-ethylidene (1,3-diphenyl-4,5-dibromo-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride are especially preferred.

  In the method for producing a ruthenium complex compound of the present invention, first, as the deprotonation step, an imidazolium salt is reacted with a deprotonating agent. The imidazolium salt is a compound represented by the general formula (10).

In formula (10), R ¹ and R ² represent the same meaning as in general formula (1). Z represents an anion, and p is an integer corresponding to the anion valence of Z. Z may be any anion, but specific examples of preferred imidazolium salts include halides, sulfates, hydrogen sulfates, phosphates, hydrogen phosphates, dihydrogen phosphates, perchlorates, tetrafluorides. Examples thereof include boron salts.

  The deprotonating agent is a compound that draws out the proton at the 2-position of the imidazolium salt to produce imidazoline-2-ylidenes. Specific examples of deprotonating agents include alkali metal alkoxides such as potassium tert-butoxide; alkali metals such as sodium and potassium; alkali metal hydrides such as sodium hydride and potassium hydride; lithium diisopropylamide, potassium bis (trimethylsilyl) ) Alkali metal amides such as amide and sodium bis (trimethylsilyl) amide; alkyllithiums such as n-butyllithium; Of these, potassium tert-butoxide is preferable.

  The reaction is carried out by mixing an imidazolium salt and a deprotonating agent in an organic solvent under an inert gas atmosphere such as argon or nitrogen. Any organic solvent can be used as long as it does not affect the reaction in the deprotonation step and the halogen substitution step and ligand exchange step described later. Among them, a solvent in which the product ruthenium complex compound (A) is soluble is preferable. The ruthenium complex compound (A), the raw material imidazolium salt, the deprotonating agent, the halogenating agent and neutral ligand described below. Particularly preferred are ruthenium compounds having a solvent and a solvent in which the intermediate product in each step is soluble. By using such a solvent, the isolated and purified ruthenium complex compound (A) can be easily isolated. Examples of such an organic solvent include aromatic hydrocarbons such as benzene and toluene; ethers such as tetrahydrofuran, diethyl ether and anisole; ketones such as acetone and methyl ethyl ketone; ethers are particularly preferable.

  The amount of the imidazolium salt and the deprotonating agent to be used is a molar ratio of imidazolium salt: deprotonating agent and is usually 1: 0.5 to 1:10, preferably 1: 1 to 1: 5. The reaction temperature is usually from −100 ° C. to + 100 ° C., and the reaction time is usually from 1 minute to 1 hour.

The production method of the present invention includes a halogen substitution step in which a halogenating agent is added and reacted subsequent to the deprotonation step.
The halogenating agent is a compound that halogenates positions 4 and 5 of imidazoline-2-ylidenes, and a compound having a nucleophilic halogen is used. Specific examples of such compounds include carbon tetrafluoride, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, chlorotrifluoromethane, bromotrifluoromethane, iodotrifluoromethane, bromotrichloromethane, 1,1,1. -Halogenated carbon such as trichloro-2,2,2-trifluoroethane, chloropentafluorobenzene, 1,1,1-tribromo-2,2,2-trifluoroethane, bromopentafluorobenzene; N-chloro amber Succinimides such as acid imide and N-bromosuccinimide; among them, halogenated carbon is preferable, carbon tetrafluoride, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, Chlorotrifluoromethane, bromotrifluoromethane, iodotrifluoromethane and bromotrichlorometa It is more preferable. Carbon tetrachloride and carbon tetrabromide are particularly preferred from the viewpoint of high reactivity and easy handling, and carbon tetrabromide is most preferred because it is low in volatility and hardly causes environmental problems.

  The amount of the halogenating agent used is a molar ratio with the imidazolium salt, and the imidazolium salt: halogenating agent is usually 1: 1 to 1: 5, preferably 1: 1.5 to 1: 2.5, Most preferably, it is 1: 1.8-1: 2.2. If the amount of the halogenating agent is too small, the yield decreases, and if it is too large, the substituted imidazoline-2-ylidene may be decomposed. The reaction temperature is usually from −100 ° C. to + 100 ° C., and the reaction time is usually from 1 minute to 1 hour.

In the manufacturing method of this invention, it has the ligand exchange process made to add and react the ruthenium compound which has a neutral ligand following a halogen substitution process.
The neutral ligand may be any ligand having a neutral charge, that is, a Lewis base. Specific examples thereof include oxygen atom, water, carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, phosphinites, phosphites, stibines, sulfoxides, thioethers, amides, Aromatic compounds, cyclic diolefins, olefins, isocyanides, thiocyanates, carbene compounds and the like can be mentioned.

  Specific examples of ruthenium compounds having a neutral ligand include carbonyl (dihydrido) tris (triphenylphosphine) ruthenium (II), chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium (II), dichloro (benzene ) Ruthenium, cis-dichlorobis (2,2′-bipyridine) ruthenium (II), dicarbonylcyclopentadienylruthenium (II), di-μ-chlorobis (p-cymene) chlororuthenium (II), dichloro (1, 5-cyclooctadiene) ruthenium (II), dichlorodicarbonylbis (triphenylphosphine) ruthenium (II) dichlorotricarbonylruthenium, dichlorotris (triphenylphosphine) ruthenium (II) and the like.

  Further, in order to obtain a ruthenium complex compound suitable for metathesis reaction, particularly metathesis ring-opening polymerization of norbornene-based monomers, it is preferable to use a ruthenium compound having a ruthenium-carbene structure. Specifically, a ruthenium compound having a structure in which a substituted imidazoline-2-ylidene is substituted with a phosphine in the ruthenium-carbene complex compound represented by the general formula (2) is preferable, and the general formulas (3) to (9) A ruthenium compound having a structure in which a substituted imidazoline-2-ylidene is substituted with a phosphine in the ruthenium-carbene complex compound represented by the formula:

  The amount of the ruthenium compound having a neutral ligand is a molar ratio with the imidazolium salt, and the imidazolium salt: ruthenium compound is usually 1: 0.1 to 1:10, preferably 1: 0.2. ~ 1: 2. The reaction temperature is usually from −100 ° C. to + 100 ° C., and the reaction time is usually from 1 minute to 1 hour.

  In the production method of the present invention, the deprotonation step, the halogen substitution step and the ligand exchange step are performed in one pot. According to the production method of the present invention, since it is not necessary to isolate and produce an intermediate product in each step, the ruthenium complex compound (A) can be produced simply and efficiently.

  The method for isolating and purifying the ruthenium complex compound (A) is not particularly limited, and a conventionally known recrystallization method or the like can be employed. Moreover, you may employ | adopt the process which precipitates this compound (A) by adding the organic solvent insoluble in the ruthenium complex compound (A) following the said ligand exchange process. Examples of the organic solvent in which the ruthenium complex compound (A) is insoluble include alcohols such as methanol and aliphatic hydrocarbons such as n-hexane. Prior to the addition of the organic solvent, the reaction mixture may be concentrated if necessary. According to this method, since only the ruthenium complex compound (A) can be selectively precipitated, the isolation and purification of the compound (A) are extremely easy and preferable. Of course, it may be further washed with an insoluble solvent or may be purified by recrystallization.

  The ruthenium complex compound (A) can be suitably used as a catalyst for metathesis reactions of olefin compounds. The olefin compound is not particularly limited as long as it has at least one carbon-carbon double bond in the molecule. Further, the ruthenium complex compound (A) exhibits high activity also with respect to an olefin compound having a polar group. Examples of the polar group include functional groups containing a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, and the like.

  More specifically, alkoxyl group, carboxyl group, alkenyloxy group, alkynyloxy group, aryloxy group, alkoxycarbonyl group, alkylthio group, arylthio group, alkylamino group, arylamino group, alkylamide group, arylamide group, Functional groups such as alkylsilyl group, arylsilyl group, alkylsulfonyl group, alkylsulfinyl group, nitro group, nitroso group and cyano group can be mentioned.

  The metathesis reaction of an olefin compound includes all of the reactions generally referred to as olefin metathesis reactions (see KJ Ivin and JC Mol, Olefin Metathesis and Metathesis Polymerization, Academic Press, Tokyo, etc.). For example, ring-opening metathesis polymerization, ring-closing metathesis reaction, cross-metathesis reaction of acyclic olefin, metathesis polymerization of acyclic diene and the like can be mentioned.

  The metathesis reaction can be carried out without solvent or in a solvent. The solvent to be used can be appropriately selected depending on the type of olefin compound to be reacted. However, since the ruthenium complex of the present invention is stable not only in a nonpolar solvent but also in a polar solvent, not only a nonpolar solvent but also a polar solvent can be used. it can.

  Examples of nonpolar solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydro Alicyclic hydrocarbons such as naphthalene, bicycloheptane, tricyclodecane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene, and tetrahydronaphthalene can be used. Examples of polar solvents include nitro compounds such as nitromethane and nitrobenzene; nitrile compounds such as acetonitrile and benzonitrile; ethers such as diethyl ether and tetrahydrofuran; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol. Alcohols such as t-butyl alcohol; water and the like can be used. Among these, it is preferable to use chain aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, alcohols, and water that are widely used industrially.

  In the metathesis reaction, the mixing ratio of the olefin compound and the solvent is not particularly limited, but the concentration of the olefin compound in the reaction solution is usually 1 to 100% by weight, preferably 2 to 100% by weight, more preferably 5 to 100% by weight. Range. When the olefin compound concentration is 1% by weight or less, the productivity of the reaction product is lowered.

  The metathesis reaction can be initiated by mixing the olefin compound and the ruthenium complex compound (A). The amount of the ruthenium complex compound to be used relative to the olefin compound is not particularly limited, but is usually 1: 100 to 1: 2,000,000, preferably 1 in terms of a molar ratio of (metal ruthenium in the catalyst) :( olefin compound). : 500 to 1,000,000, more preferably in the range of 1: 1,000 to 1: 500,000. If the amount of catalyst used is too large, catalyst removal becomes difficult. On the other hand, if the amount of catalyst is too small, sufficient reaction activity cannot be obtained.

  The reaction temperature of the metathesis reaction can be arbitrarily selected depending on the type of metathesis reaction and the type of olefin compound to be reacted, but is usually in the range of −80 ° C. to 200 ° C. If the reaction temperature is too low, the reaction rate becomes slow, whereas if the reaction temperature is too high, the ruthenium complex compound (A) may be decomposed. The reaction time can be arbitrarily set depending on the type of reaction, but is usually in the range of 1 minute to 1 week.

  Among these metathesis reactions, the ruthenium complex compound (A) of the present invention is particularly suitable as a catalyst for a ring-opening metathesis polymerization reaction (hereinafter simply referred to as “polymerization reaction”) of a cyclic olefin.

  Examples of cyclic olefins include monocyclic olefin monomers; norbornene monomers such as norbornenes, dicyclopentadienes, tetracyclododecenes, etc., and norbornene monomers in terms of high polymerization activity. Is preferred. A cyclic olefin can be used individually or in combination of 2 or more types, respectively. These cyclic olefins may be substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or the polar group. Moreover, when using a norbornene-type monomer, you may have a double bond other than the double bond of a norbornene ring.

  Examples of the monocyclic olefin include cyclic monoolefins and cyclic diolefins having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms. Specific examples of the cyclic monoolefin include cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene and the like. Specific examples of the cyclic diolefin include cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, phenylcyclooctadiene and the like.

  As the norbornene-based monomer, substituted and unsubstituted polycyclic norbornene having 3 or more rings can be used. Specific examples thereof include norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, chlorination. Bicyclic norbornene which may have a functional group such as norbornene, ethylidene norbornene, chloromethyl norbornene, trimethylsilyl norbornene, phenyl norbornene, cyano norbornene, dicyano norbornene, methoxycarbonyl norbornene, pyridyl norbornene, nadic acid anhydride, nadic acid imide Kind;

  Dicyclopentadiene, dihydrodicyclopentadiene and its alkyl, alkenyl, alkylidene, aryl, hydroxyl, anhydride groups, dicarboximide, carboxyl, alkoxycarbonyl-substituted tricyclic norbornenes; dimethanohexahydronaphthalene, dimethano Tetracyclic norbornenes such as octahydronaphthalene and its alkyl, alkenyl, alkylidene, aryl, hydroxyl, anhydride groups, dicarboximide, carboxyl, alkoxycarbonyl substituents; pentacyclic norbornenes such as tricyclopentadiene; hexacyclohepta Hexacyclic norbornenes such as decene; dinorbornene, compounds in which two norbornene rings are bonded by a hydrocarbon or ester group, etc., and norbornene rings such as alkyl and aryl substituents thereof Compounds, and the like.

In the polymerization reaction, a polymer molecular weight regulator can be used. Examples of the molecular weight modifier include compounds having a vinyl group. Specifically, α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Halogen-containing vinyl compounds such as allyl chloride; vinyl esters such as allyl acetate and glycidyl methacrylate; vinyl alcohols such as allyl alcohol; nitrogen-containing vinyl compounds such as acrylamide and the like can be used.
Although the usage-amount of a vinyl compound can be suitably selected according to the molecular weight of the target polymer, Usually, it is the range of 0.001-20 mol% with respect to a norbornene-type monomer.

  Further, at the end of the polymerization reaction, the polymerization can be stopped by re-adding the above-described vinyl compound as desired to release the ruthenium complex compound from the growth terminal of the polymer. This polymerization termination method is particularly useful for improving the activity of the catalyst used in the hydrogenation step of hydrogenating the resulting polymer following the polymerization reaction.

  The catalyst for hydrogenation reaction of the present invention comprises a ruthenium complex compound (A). The ruthenium complex compound (A) also shows high activity as a catalyst for selectively hydrogenating the carbon-carbon double bond of the olefin compound. The olefin compound is not particularly limited as long as it has at least one carbon-carbon double bond in the molecule, and can be arbitrarily selected according to the purpose.

  As the catalyst for the hydrogenation reaction, a ruthenium-carbene complex compound and a ruthenium hydride complex compound represented by the general formula (2) are preferable because of their high activity. Specific examples of the ruthenium hydride complex include carbonyl (tricyclohexylphosphine) (1,3-dimesityl-4,5-dichloroimidazoline-2-ylidene) ruthenium (II) (hydrido) (chloride), carbonyl (tricyclohexylphosphine). ) (1,3-Dimesityl-4,5-dibromoimidazoline-2-ylidene) ruthenium (II) (hydrido) (chloride), carbonyl (tricyclohexylphosphine) (1,3-dimesityl-4,5-dichloroimidazoline- 2-Ilidene) ruthenium (II) dihydride, carbonyl (tricyclohexylphosphine) (1,3-dimesityl-4,5-dibromoimidazoline-2-ylidene) ruthenium (II) dihydride, hydrogen (tricyclohexylphosphine) (1,3 Dimesityl-4,5-dichloroimidazoline-2-ylidene) ruthenium (II) (hydrido) (chloride), hydrogen (tricyclohexylphosphine) (1,3-dimesityl-4,5-dibromoimidazoline-2-ylidene) ruthenium ( II) (hydrido) (chloride) and the like.

  The hydrogenation reaction is performed by bringing an olefin compound into contact with hydrogen in the presence of the ruthenium complex of the present invention. This hydrogenation reaction can be carried out without solvent or in a solvent. The solvent can be appropriately selected depending on the type of the olefin compound to be hydrogenated, and not only a nonpolar solvent but also a polar solvent can be used. Specifically, any of the same solvents as those for the metathesis reaction of the olefin compound described above can be used.

  Although the usage-amount of the ruthenium complex used for hydrogenation reaction is not specifically limited, When it represents with the molar ratio of (metal ruthenium in a catalyst) :( carbon-carbon double bond of an olefin compound), it is usually 1: 100-1: The range is 2,000,000, preferably 1: 500 to 1,000,000, more preferably 1: 1,000 to 1: 500,000. The pressure of hydrogen used for the hydrogenation reaction is usually 10 MPa or less, preferably 0.01 to 8 MPa, more preferably 0.05 to 5 MPa. The reaction temperature and reaction time of the hydrogenation reaction can also be appropriately selected, but the ranges are the same as in the case of the metathesis reaction of the olefin compound described above.

  In addition, after the ring-opening metathesis polymerization of the olefin compound using the ruthenium complex of the present invention, the polymer produced subsequently can be hydrogenated. In that case, the ruthenium complex compound of the present invention used as a catalyst in the polymerization step can be used as it is as a hydrogenation reaction catalyst.

  Furthermore, as a method for improving the hydrogenation reaction catalytic activity, a Lewis base such as triethylamine, N, N-dimethylacetamide, or triphenylphosphine may be added. The amount of the Lewis base to be added is not particularly limited as long as it is between 1 molar equivalent and 1,000 molar equivalents relative to the ruthenium metal.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified.

(1) The structure of the synthesized ruthenium complex compound was identified by measuring ¹ H-NMR and ³¹ P-NMR spectra using CDCl ₃ as a solvent.
(2) The polymerization conversion rate in ring-opening metathesis polymerization was determined by a solid content weight measurement method.
(3) The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer are polystyrene conversion values by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8020) using tetrahydrofuran as a solvent. As measured. Moreover, the molecular weight of the hydride of the ring-opening polymer was measured as a polystyrene conversion value by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8121, 135 ° C.) using orthodichlorobenzene as a solvent. .
(4) The hydrogenation rate of the carbon-carbon double bond in the polymer was measured by ¹ H-NMR spectrum.

Example 1: One-pot synthesis of benzylidene (1,3-dimesityl-4,5-dibromoimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (complex a) 1,3-bis (2,4,6-trimethyl) 0.58 parts of phenyl) imidazolium chloride was placed in a Schlenk tube, and the inside of the tube was replaced with argon. Then, 3 parts of tetrahydrofuran (THF) was added and stirred for 5 minutes. To this suspension solution, 0.15 part of potassium tert-butoxide was added and the reaction was continued for 30 minutes. Then, 0.27 part of carbon tetrabromide was added and the reaction was continued for another 30 minutes. Thereto was added 0.43 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride, and the reaction was continued for 1 hour. After concentrating the reaction solvent, a large amount of methanol was added to precipitate a reddish brown powder. The precipitate was collected by filtration and washed with methanol until colorless. Then, 0.33 part of complex a was obtained by drying under reduced pressure. All operations were performed at room temperature.

According to ¹ H-NMR and ³¹ P-NMR spectrum measurements of the resulting complex a, this compound was converted to benzylidene (1,3-dimesityl-4,5-dibromoimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride. I confirmed that there was. Moreover, the peak derived from an impurity was not seen in a NMR spectrum, but it has confirmed that the purity of the obtained complex a was almost 100%.
The spectrum data is shown below.
¹ H-NMR (δ ppm): 0.75-1.70 (br, 30H), 1.96 (s, 12H), 2.20 (m, 3H), 2.37 (s, 6H), 5. 93 (br, 1H), 6.75 (br, 1H), 7.06 (s, 2H), 7.12 (t, 2H), 7.40 (t, 1H), 8.94 (br, 2H) ), 19.4 (s, 1H)
³¹ P-NMR (δ ppm): 31.3

Example 2: One-pot synthesis of benzylidene (1,3-dimesityl-4,5-dichloroimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride (complex b) 1,3-bis (2,4,6-trimethyl) Complex b0 in the same manner as in Example 1 except that 0.3 part of phenyl) imidazolium chloride and 10 parts of THF were used, and 0.27 part of carbon tetrachloride was used instead of carbon tetrabromide. .32 parts were obtained.

According to ¹ H-NMR and ³¹ P-NMR spectrum measurements of the resulting complex b, this compound was converted to benzylidene (1,3-dimesityl-4,5-dichloroimidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride. I confirmed that there was. Moreover, the peak derived from an impurity was not seen in a NMR spectrum, and it has confirmed that the purity of the obtained complex b was almost 100%.
The spectrum data is shown below.
¹ H-NMR (δ ppm): 0.75-1.70 (m, 30H), 1.96 (s, 12H), 2.21 (m, 3H), 2.37 (s, 6H), 5. 94 (br, 1H), 6.75 (br, 1H) 7.08 (s, 2H), 7.12 (t, 2H), 7.41 (t, 1H), 8.93 (br, 2H) 19.4 (s, 1H)
³¹ P-NMR (δ ppm): 31.5

Example 3
In an autoclave equipped with a stirrer, 430 parts of cyclohexane and 150 parts of dicyclopentadiene (DCP) were added, and 1.4 parts of 1-hexene was added as a molecular weight regulator. To this solution, a catalyst solution in which 0.01 part of the complex a obtained in Example 1 was dissolved in 15 parts of toluene was added to initiate the polymerization reaction. After reacting at 60 ° C. for 1 hour, 0.01 part of ethyl vinyl ether was added to terminate the polymerization reaction. When a part of the polymerization reaction solution was collected and analyzed, a DCP ring-opened polymer was obtained with a polymerization conversion rate of 99% or more. The polymer had Mn of 12,200 and Mw of 25,800.

  Next, after adding 0.012 part of triethylamine, hydrogen was supplied into the autoclave and stirred at 165 ° C. and a hydrogen pressure of 5 MPa for 6 hours to conduct a hydrogenation reaction. The hydrogenation rate of the obtained DCP ring-opening polymer hydride was 99.9% or more, Mn was 15,200, and Mw was 34,100.

Example 4
In an autoclave equipped with a stirrer, 430 parts of cyclohexane and 150 parts of 8-ethyltetracyclododecene (ETCD) were charged, and 1 part of 1-hexene was added as a molecular weight regulator. To this solution, a catalyst solution in which 0.007 part of the complex b obtained in Example 2 was dissolved in 15 parts of toluene was added to initiate the polymerization reaction. After reacting at 60 ° C. for 1 hour, 0.007 part of ethyl vinyl ether was added to terminate the polymerization reaction. When a part of the polymerization reaction solution was collected and analyzed, an ETCD ring-opening polymer was obtained with a polymerization conversion rate of 99% or more. The polymer had Mn of 16,500 and Mw of 39,300.

  Then, after adding 0.008 part of triethylamine, hydrogen was supplied into the autoclave, and the mixture was stirred at 165 ° C. and a hydrogen pressure of 5 MPa for 6 hours to carry out a hydrogenation reaction. The hydrogenation rate of the obtained ETCD ring-opening polymer hydride was 99.9% or more, Mn was 18,700, and Mw was 42,200.

Example 5
To an autoclave equipped with a stirrer, 430 parts of THF, 75 parts of ETCD and 75 parts of norbornene-5,6-dicarboxylic anhydride (NDCA) were charged, and 1 part of 1-hexene was added as a molecular weight regulator. To this solution was added a catalyst solution in which 0.07 part of the complex a obtained in Example 1 was dissolved in 15 parts of THF. After stirring the solution at 60 ° C. for 1 hour, 0.07 part of ethyl vinyl ether was added to terminate the polymerization reaction. When a part of the polymerization reaction solution was collected and analyzed, a ring-opening copolymer of ETCD and NDCA was obtained at a polymerization conversion rate of 99% or more. The copolymer had Mn of 15,300 and Mw of 29,800.

  Next, 0.08 part of N, N-dimethylacetamide was added, hydrogen was supplied into the autoclave, and the mixture was stirred at 165 ° C. and a hydrogen pressure of 5 MPa for 6 hours to carry out a hydrogenation reaction. The hydrogenation rate of the obtained ring-opening copolymer hydride was 99.9% or more, Mn was 18,900, and Mw was 45,000.

Example 6
The polymerization reaction was carried out in the same manner as in Example 5 except that 0.07 part of complex b was used instead of complex a. When a part of the polymerization reaction solution was collected and analyzed, a ring-opening copolymer of ETCD and NDCA was obtained at a polymerization conversion rate of 92%. The copolymer had an Mn of 13,200, an Mw of 27,600, and a copolymerization ratio of ETCD: NDCA = 55: 45 by weight.

  As is clear from the above examples, according to the method of the present invention, a ruthenium complex compound (A) having a substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with a halogen atom as a ligand is simple and efficient. It turns out that it can manufacture well. Further, the obtained ruthenium complex compound (A) exhibited high activity as a catalyst for the ring-opening metathesis polymerization reaction and hydrogenation reaction of norbornene monomers.

Claims (5)

A catalyst for ring-opening metathesis polymerization of a norbornene-based monomer comprising a ruthenium complex compound (A) having a substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with a halogen atom as a ligand. 4- and 5-positions ruthenium complex compound (A1) norbornene monomer ring-opening metathesis polymerization catalysts of which comprises a having a substituted imidazolin-2-ylidene substituted with a bromine atom as a ligand. A process for producing a norbornene-based ring-opening polymer, wherein a norbornene-based monomer is polymerized in the presence of the catalyst for ring-opening metathesis polymerization according to claim 1 or 2 . The method according to claim 3, wherein the norbornene monomer has a polar group. A catalyst for hydrogenation reaction of an olefin compound comprising a ruthenium complex compound (A) having a substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with a halogen atom as a ligand.